Anthraquinone dyestuffs



United States l atent 2,768,183 ANTHRAQUINONE DYESTUFFS Milton L. Hoefle, Roseville, Mich., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application August 4, 1954, Serial No. 447,886

5 Claims. (Cl. 260-377) This invention relates to the production of a new series of anthraquinone dyestuffs and to mixtures of such dyestuffs with other anthraquinone dyestuffs.

The problem of providing acid gas resistant dyestuffs in the blue range for cellulose acetate rayon fibers and other fibrous material having a basis of polymeric material has long been recognized. Dyestuffs of the amino anthraquinone series have up to the present time found widespread acceptance for such use, but in almost all instances, the blue colorations heretofore obtained do not have perfect resistance to acid gas fumes, the action of which in general produces reddening and dulling of the shade to an undesirable extent. While reddish-blue shades may per se be acceptable and even desirable in some instances, such shades are in general associated in the consumers mind with undesirable fading.

It is an object of this invention to provide a dyestuff composition capable of dyeing acetate rayon and other film and fibrous materials in blue shades having sub.- stantially no tendency to fade to reddish tinges app -ea:

posure to acid gas fumes andother deleterious influences.

Another object of this inventionis to provide a new series of anthraquinone dyestuffs which may be employed for producing such dyestufi mixtures, Qther objects and advantages of this invention appearfrom the follow? ing'description.

The attainment of the above objects is made possible by the present invention which broadly comprises the provision of a composition comprising a blue anthraquinone dyestuff subject to changing to reddish hues upon exposure to acid gas fumes and a blue anthraquinone dyestuff subject to changing to greenish huesppon exposure to acid gas fumes. In this manner, the meddish hues are counterbalanced by the greenish hues acquired by the components of the composition "uponexposure to acid gas fumes, whereby the original blue shade ,of {the dyeings, remains unaltered, though a .dulling may in some instances be discernible.

a further f tu e o his i v ntion a mew eries, of amino anthraquinone dyestuffs have been found: high possess the desirable property qf produeing blue shades in y ns w i ad acq re ee h hue a n neze posure to acid gas fumes. This new series ;of.-d ufis comprise compounds having the following fonnpl wherein Y is selected from the group consisting of CN and--CO.NH.( RO )nX, R 1is=rlowersalkyl,.X is selected from thelgroup consisting ,of Hand glower-alkyl, and n has a value of zero to 3. In this formula, the term tion also.

lower alkyl includes such radicals as methyl, ethyl, propyl, isopropyl, and the like. It will be understood that in any particular compound included within the scope of the above depicted formula, tlie defined substituents in the l, 2 and 4-positions inay'have the same or different values within the ranges stated:

The compounds of the above formula may be made several different methods. In the following description of such methods, Y, R, X and n have the values given above.

I. An aminoanthraquinone having a formula as illustrated above except for 'a halide or sulfonic acid group in the 2-position is reacted with respectively CuCN or a water-soluble salt of hydrocyanic acid such as sodium cyanide, potassium cyanide, ammonium cyanide, etc., to replace the halide or sulfonic acid radical with a nitrile radical. Depending upon the starting components and the operating conditions, the resulting products may include compounds containing a nitrile group in the 3-posi- II. aminoanthraquinone having a formula as illustrated above except for a reactive radical such as halide.

(C1 or Br), N02, alkoxy or aryloxy in the 4-position is reacted with an arylamine of the formula:

This condensation may be carried out if desired in the presence of catalysts such as copper, cuprous or cupric salts, and/or acid binding agents such as sodium carbonate, bicarbonate or acetate and/or in an inert inorganic or organic solvent or diluent.

III. An aminoanthraquinone having ,a formula as illus trated above except for a reactive radical such as halide (C1 or Br), N02 alkoxy or aryloxy in the 1-position is reacted with an amine of the formula H2N(RO)11.X-

IV. An aminoanthraquinone having a formula as illustrated above except for a carboxylic acid halide or ester group in the 2-position is reacted with an amine of the formula H2N(RO)nX to produce the corresponding carboxamide.

V. aminoanthraquinone having a formula as illustrated above except for a nitro group in the '1 position is subjected to reduction, followed if desired by reaction with av-compound containing the group (RO)1tX joined to ;a reactive radical.

Y1. An aminoanthraquinone having a formula as illustrated above containing a nitrile group in 2-position is subjected to controlled hydrolysis (in view of the secondary amino groups present in 1 and 4-posi tion) to produce the corresponding carboxamide, followed if ,desired by reaction with a compound having the group (RO)X joined to a reactive radical.

Other methods of producing the compounds of this invention will become ,apparent to .the person skilled in the art. Similarly, it will beobvious that in certain instances sensitive radicals or groups already present in the intermediates from which the compounds of this invention are produced must be :blocked or protected during the ,reaction.

Besides the property of acquiring ,a greenishhueupon exposure .to acid gas fumes, the above described compounds of this invention have good lightand washfastness properties and good substantivity for the material to be colored. -In addition to cellulose acetate, .the dyestuffs :of this invention may ,be employed for a coloring other :natural ,or synthetic polymeric material .in .bulk, film or fiber form, including polyarnides, polyesters, and

polyacrylonitriles and the like, such as nylon, Orlon, Dacron, Acrilan, Dynel, and the like.

The aforementioned compounds may be mixed in any required proportions with known blue anthraquinone dyestulfs subject to changing to reddish hues upon exposure to acid gas fumes. The proportions of the compounds of this invention to be employed in such mixtures will of course be dependent upon the quantum of reddish hues to be neutralized or compensated for, which in turn is dependent upon the number, types and amounts of anthraquinone dyestuffs in the mixtures producing such reddish hues, the material being dyed and the like. In general, blue anthraquinone dyestuif mixtures containing proportions of about 25 to 75 parts by weight of the compounds of this invention and about 75 to 25 parts by weight of at least one other anthraquinone dyestufi subject to changing to reddish hues upon exposureto acid gas fumes will produce satisfactory blue shades which are substantially unaffected by exposure to acid gas fumes.

The following examples in which parts are by weight unless otherwise indicated, will serve to illustrate the invention, but they are not intended to limit it thereto.

Example 1 Into a stirred autoclave were placed 20.0 parts l-amino- 4 (a-hydroxy-6-methoxy-m-toluidino)2-anthraquinonesulfonic acid, prepared by the condensation of bromamine acid and 5-amino-4-rnethoxybenzyl alcohol [the latter compound may be produced by'the process described in Ber. 34, 2459 (1901)], 11.0 parts potassium cyanide and 500 parts water. The contents of the autoclave were then heated at 140 C. for eight hours. The reaction mixture was then filtered, thoroughly washed with hot water until the filtrate was colorless, and dried. The final weight of the dried blue powder obtained was 12.3 parts. It dyed rayon acetate in bright blue shades which became green when exposed to the action of gas combustion fumes. The structure is shown below.

CHzOH ll NH Example 2 The same procedure as outlined in Example 1 was used except that the 20.0 parts of 1-amino-4-(u-hydroxy-6- methoxy-m-toluidino)2-anthraquinonesulfonic acid were replaced by 20.0 parts of 1-amino-4[a-(2-hydroxyethyl)- 6-methoxy-m-toluidino] 2 anthraquinone sulfonic acid. The product possessed properties similar to those indicated in Example 1. The structure is shown below.

o NH;

011,0 omomofl Example 3 Into a reaction vessel equipped with a stirrer, thermometer and reflux condenser were charged 10.0' parts N'- (Z-hydroxyethyl) 1 (2 hydroxyethylamino);4-bromo- 2-anthraquinonecarboxamide, 7.5 parts 5-amino-4-methoxybenzyl alcohol, 5.0 parts sodium carbonate, 5.0 'parts sodium bicarbonate, 0.5 part cuprous chloride, 150 parts water and 25 parts ethanol. The resulting mixture was heated at reflux for eight hours. It was then cooled,

filtered, and washed with 200 parts hot water (65 0.).

Upon drying, 7.4 parts of product were obtained which dyed cellulose acetate a bright blue-green shade, which when exposed to the action of combustion gas fumes became bright green. The structure is shown below:

Example 4 CHgO CHZCHQOH Example 5 Equal amounts of the product from Example 1 and 1amino-4-cyclohexylamino-2-anthraquinonecarboxamide were intimately mixed and the resulting mixture was dispersed in the usual manner. The resulting dyestufi mixture dyed cellulose acetate in blue shades which upon exposure to the action of combustion gas fumes dulled slightly but remained practically the same shade.

Example 6 In Example 5 above the 1amino-4-cyclohexylamino-2- anthraquinonecarboxamide was replaced by an equal Weight of 4,8dimethylaminoanthrarufin. In this case also, the gas fastness of the resulting mixture was much improved over the gas fastness of the two components when they were dyed separately.

Example 7 I claim: 1. Compounds having the formula c NH(RO)X arm- Rom:

wherein Y is selected from the group consisting of CN and CONH-(ROMX, R is lower alkyl, X is selected from the group consisting of H and lower alkyl, and n has a value of zero to 3.

2. A compound having the formula 3. A compound having the formula A In CHa)

(IJHZOCH2CHZOH 4. A compound having the formula 5. A compound having the formula References Cited in the file of this patent UNITED STATES PATENTS Seymour Feb. 26, 1952 

1. COMPOUNDS HAVING THE FORMULA 